WO2021233780A1

WO2021233780A1 - Method for the control of pressure in a loop for the preparation of ammonia or methanol

Info

Publication number: WO2021233780A1
Application number: PCT/EP2021/062829
Authority: WO
Inventors: Christian Henrik SPETH; Michael Hultqvist; Pat A Han
Original assignee: Haldor Topsoe AS
Current assignee: Topsoe AS
Priority date: 2020-05-18
Filing date: 2021-05-14
Publication date: 2021-11-25
Anticipated expiration: 2022-11-18
Also published as: EP4153536A1; CN115551806A; JP2023526396A; KR20230012492A; US20230137755A1; TWI895401B; AU2021276065A2; TW202212261A; AU2021276065A1; MX2022014171A; BR112022023398A2; IL298249A; CA3179921A1; CL2022003202A1; PE20230810A1

Abstract

Method for the control of pressure in a loop for the preparation of ammonia or methanol by means of an anti-surge control valve of a compressor and/or a compressor flow regulation valve for the recirculation of loop recirculation gas at variating flow supply of fresh synthesis gas.

Description

Title: Method for the control of pressure in a loop for the preparation of ammonia or methanol

The present invention is directed to the method for the control of pressure in a loop for the preparation of ammo nia or methanol. More particular, the invention makes use of the anti-surge control valve of a compressor and/or a compressor flow regulation valve for the recirculation of an ammonia or methanol loop recirculation gas at variating flow of fresh ammonia or methanol synthesis gas.

As an example, ammonia synthesis gas is conventionally pre pared by subjecting hydrocarbon feed of natural gas or higher hydrocarbons to endothermic steam reforming reac- tions in a fired tubular steam reformer by contact with a steam reforming catalyst. The primary reformed gas is then fed into a secondary adiabatic reformer, wherein part of hydrogen and residual amounts of hydrocarbons in the gas are partial oxidized with air or oxygen enriched air in presence of a secondary reforming catalyst. From the sec ondary reformer, raw synthesis gas containing hydrogen, ni trogen, carbon monoxide and carbon dioxide formed during reaction of the feedstock in the above steam reforming re actions and nitrogen introduced into the gas through addi- tion of air in the secondary reforming step.

The primary and secondary steam reforming can in large scale ammonia or methanol synthesis plants be replaced by autothermal reforming (ATR).

Recently, use of renewable energy in the ammonia or metha nol synthesis has become more available. As an example, combination of electrolysis of water operated on renewable energy, such as wind power and solar energy for the produc tion of hydrogen by electrolysis of water and air separa tion for the production of nitrogen has been envisaged for the preparation of ammonia synthesis gas. The thus produced hydrogen and nitrogen are combined in stoichiometric ratios to form synthesis gas for ammonia production.

The problem when using renewable energy in the ammonia or methanol synthesis is that the supply of energy variates depending on the natural variations of for instance wind and sun. As a result, the flow of fresh methanol or ammonia synthesis gas produced by means of renewable energy can variate substantially.

Because of relatively low single pass conversion rates of ammonia or methanol synthesis gas in in the respective con verters caused by equilibrium limitations, a large loop re cycle stream of unconverted synthesis gas is required in the loops.

To substitute converted hydrogen and nitrogen in the uncon verted synthesis gas, a make-up gas of fresh ammonia syn thesis gas must constantly be added into the loop recycle gas. Similar, to the ammonia synthesis, converted hydrogen and carbon oxides must be substituted in the methanol syn thesis loop with fresh hydrogen and carbon oxides contain ing synthesis gas. In case of large and frequent load variations because of variating flow of fresh synthesis gas to the synthesis loop, the mechanical stress caused by pressure variations introduced by the load variations will lead to unreferenced mechanical stress conditions that may cause mechanical failures of pressure bearing equipment. The temperature variations, however, will be limited.

Such operating conditions are especially relevant when the production is dependent on a variable flow of feedstock such as it is the case for green ammonia or methanol pro duction.

Traditionally an ammonia and methanol loop does not feature a dedicated pressure control. In case of reduced feed flow to the loop, the loop pressure will drop. Thereby the con version will reduce to a point eventually matching the make-up flow. In case of increasing feed flow, the pressure and the conversion will increase. Since the load of a tra ditional ammonia and methanol plants tends to be stable over long periods, the absence of a pressure control does not normally represent a problem.

For a given ammonia converter/loop configuration a possible way to control the loop pressure is variating the H/N ratio in the in the fresh ammonia synthesis gas, i.e. the make-up gas can to decrease the reactivity of the gas. In some cases, it is also possible to vary the contents of inerts in the loop by reducing the purge flow, but this is seldom relevant for green ammonia production where the make-up gas is very low in inerts. In practice, however, it is diffi cult to control loop pressure with this method. We have found that the amount of feed gas to the to the am monia and methanol reactor can be controlled by the anti surge control of the recirculator (loop recycle compres sor). The antisurge or kickback valve is typically a fast reacting control element for protection against surge re sulting in vibrations and thus damage of the compressor.

Pursuant to the above finding, the present invention pro vides a method for the control of pressure in a loop for the preparation of ammonia or methanol comprising the steps of

(a) providing a fresh ammonia or methanol synthesis gas;

(b) providing a loop recirculation gas;

(c) providing a loop recirculation compressor with an anti- surge valve and/or a compressor flow regulation valve;

(d) providing an ammonia or methanol synthesis loop;

(e) adding the fresh ammonia or methanol synthesis gas into the loop recirculation gas;

(f) pressurizing the loop recirculation gas from step (e) in the loop recirculation compressor; and

(g) monitoring pressure in the ammonia or methanol synthe sis loop, wherein flow of the loop recirculation gas through the anti-surge valve and/or the recirculation compressor flow regulation valve is controlled to obtain a substantially constant pressure in the ammonia or methanol synthesis loop.

In case of slow load variation (days or weeks), the method according to the invention can be supplemented by control of the temperature in a high pressure ammonia or methanol loop separator. Thereby reactivity of the loop recircula tion loop gas flowing to the ammonia converter can be re duced when the concentration of ammonia in the feed gas is increased. Higher temperature leads to less reactivity and higher loop pressure.

Thus, in an embodiment of the invention the method com prises the further step of controlling temperature in a loop separator arranged in the loop for the preparation of ammonia or methanol.

The loop separator separates liquid ammonia or methanol product from the unconverted gas effluent from the synthe sis converter at equilibrium between gas and liquid at the given pressure and temperature. At constant pressure and higher temperature gives higher content of product in un converted gas to be recycled back to the synthesis con verter. This will lower the potential conversion per pass since the synthesis reaction is limited by equilibrium re- suiting in reduced capacity of the synthesis loop at con stant pressure.

One of the advantages of the invention is thatenergy for operating various equipment for the preparation of ammonia synthesis gas can be renewable energy generated by wind mills, solar cells, hydraulic energy or other renewables.

Preferably, the equipment comprises one or more electroly sis units, such as solid oxide electrolysis cells. Thus, in an embodiment of the invention, hydrogen contained in the fresh ammonia or methanol synthesis gas is provided by means of electrolysis of water.

In further an embodiment, nitrogen contained in the fresh ammonia synthesis gas is provided by means of air separa tion.

In still an embodiment of the invention, the fresh methanol synthesis gas is provided by co-electrolysis of water and carbon dioxide.

In further an embodiment of the invention, the fresh ammo nia synthesis gas is prepared in a solid oxide electrolysis cell of water and air.

Fig. 1 shows a typical configuration of the make-up gas compressor, recirculator and synthesis loop.

If the antisurge valve is open, then less flow will pass on to the reactor. During start-up where the synthesis reactor is heated up by circulating gas in the loop and having the start-up heater ignited then the antisurge will initially be fully open in order to protect the recirculator from surge and to reduce the flow rate to the reactor for easy control of the heating up phase.

The same valve (antisurge valve) is used simultaneously as compressor protection and flow control valve to the reac tor. This is feasible as the two functions are never con tradictory and in any case the machine protection will overrule all other set point to the valve. This concept is well proven for start-up of the synthesis.

Using renewable energy for production of synthesis gas will provide fluctuations throughout a day in feed gas flow rate resulting in many and possibly also abrupt synthesis pres sure fluctuations. This can be smoothed out or even elimi nated by the method according to the invention. In normal operation, the recirculator antisurge valve can be used for control of the loop pressure. At full capacity the valve will remain closed and if less make up gas is available then the recirculation gas flow will be reduced correspondingly by controlled opening of the valve.

This will limit the conversion of synthesis gas in the loop to exactly the amount of make-up gas available resulting in keeping the same amount of gas in the loop and thus con stant loop pressure.

There might be an understanding of the loop pressure is also controlled by the make-up compressor speed, but this is not the case as the make-up gas compressor will deliver the required pressure for a given conversion in the loop.

Since the method of the invention controls the conversion in the loop to maintain a constant loop pressure then the make-up gas compressor will follow the loop requirement.

The only way the make-up gas compressor can do that and still be within its operating window (flow versus discharge pressure) is by opening its own antisurge valve(s) to com pensate for the lower make-up gas flow available (see fig ure 1 and 2). There could be cases where it is not allowed to use the an tisurge valve for loop pressure control valve. Then the al ternative would be to install a control valve in parallel without jeopardizing the compressor surge protection as the antisurge valve opening is still governed by the compressor requirement measured as resulting flow from two control valves to the suction of the recirculator (see Fig. 2).

Since the conversion equilibrium temperature remains con stant, a control which ensure the ratio between make-up gas and converter feed gas remains constant will nearly elimi nate pressure and temperature fluctuations in the converter and ammonia loop.

Because the anti-surge valve has a security function, the flow from the compressor discharge side to suction side may additionally or completely be regulated by means of com pressor flow regulation valve during feed gas flow varia tions. The examples of Fig. 1 and 2, will have a limitation on the turn down of the gas flow since the minimum flow to the converter will depend on the pressure drop ratio between the converter and the anti-surge valve. Fig. 3 shows a configuration where the gas flow to the con verter can be controlled down to a zero flow by means of a loop pressure controller and optionally a small bypass valve. When reducing or closing the loop pressure control ler, the synthesis gas in the synthesis reactor is retained in the reactor and maintains the reactor pressure. This will allow the loop pressure to be controlled down to very low load and still keep the loop pressure up and the con verter in hot conditions. This is important in the case where suddenly the renewable energy and thus synthesis gas production comes back from low load to high load, then the conversion of synthesis gas into ammonia or methanol can take place essentially instantaneous.

Fig. 4 shows a similar process layout as shown in Fig. 3, where one or more valves are foreseen to control converter inlet flow, recirculator anti-surge flow, and make-up gas compressor anti-surge flow. The module of the make-up gas is controlled by a ratio controller of hydrogen and nitro gen flow in ammonia synthesis gas by controlling the nitro gen flow rate relative to the hydrogen flow rate. With many fluctuations perhaps daily in energy supply, and thus di- rectly impacting the hydrogen flow rate and also the nitro gen flow rate, the measurement of hydrogen and nitrogen flow might get a bit off set at each fluctuation. A small change in the make-up gas module will be amplified in the module of the loop recirculation gas and for this reason it is desirable to improve the module controller by having a near real-time analyzer on the make-up gas. Typically, a common gas chromatography analyzer is used for multiple sampling point leading to long tubing from each sampling point to the analyzer, which results in long cycle time for each analysis. Long cycle time of 10-20 min. is not suita ble for adjustment of the module controller. A real-time analyzer can provide a cycle time of 10-20 sec. and the module controller can act in time before a wrong module gets amplified in the loop resulting in loss of capacity and/or pressure increase when high capacity is required. In the figures, A defines an analysis point, F a flow measurement point, and P a pressure measurement point.

Claims

1. Method for the control of pressure in a loop for the preparation of ammonia or methanol comprising the steps of (a) providing a fresh ammonia or methanol synthesis gas;

(b) providing a loop recirculation gas;

(c) providing a loop recirculation compressor with an anti surge valve and/or a compressor flow regulation valve;

(d) providing an ammonia or methanol synthesis loop; (e) adding the fresh ammonia or methanol synthesis gas into the loop recirculation gas;

(g) monitoring pressure in the ammonia or methanol synthe- sis loop, wherein flow of the loop recirculation gas through the anti-surge valve and/or the recirculation compressor flow regulation valve is controlled to obtain a substantially constant pressure in the ammonia or methanol synthesis loop.

2. The method of claim 1, wherein compressor flow regula tion valve is arranged in parallel with the antisurge valve.

3. The method of claim 1 or 2, wherein flow of the fresh ammonia or methanol synthesis gas is controlled by an anti surge valve of a compressor for the fresh synthesis gas.

4. The method of any one of claims 1 to 3, comprising the further step of controlling temperature in a high-pressure loop separator arranged in the loop for the preparation of ammonia or methanol.

5. The method of any one of claims 1 to 4, wherein hydro- gen in the fresh ammonia or methanol synthesis gas is pro vided by means of electrolysis of water.

6. The method of claim 5, wherein the electrolysis of wa ter is performed in a solid oxide electrolysis cell.

7. The method of claim 1 to 4, wherein the fresh methanol synthesis gas is provided by co-electrolysis of water and carbon dioxide.

8. The method of any one of claims 1 to 6, wherein nitro gen in the fresh ammonia synthesis gas is provided by means of air separation.

9. The method of any one of claims 1 to 4, wherein the fresh ammonia synthesis gas is prepared of water and air in a solid oxide electrolysis cell.

10. The method of any one of claims 1 to 9, wherein flow of the loop recirculation gas is additionally controlled by a loop pressure controller downstream or upstream the re circulation compressor.

11. The method of any one of claims 1 to 10, wherein the module of the fresh ammonia synthesis gas is controlled by a ratio controller of hydrogen and nitrogen flow in ammonia synthesis gas by controlling the nitrogen flow rate rela tive to the hydrogen flow rate.

12. The method of claim 11, wherein the ratio controller is compensated by a real-time analyzer.